IS : 4518 ( Part II ) - 1971 Indiun Standard ( Reaffirmed 2002 ) METHODS OF TEST FOR STYRENE-BUTADIENE RUBBERS PART II DETERMINATION OF SOLVENT EXTRACT AND OIL CONTENT ( Second Reprint NOVEMBER 1996 ) UDC 678.746.22-136.22 : 543 : 542.61 0 Copyright 1972 BUREAU MANAK OF INDIAN STANDARDS ZAFAR MARG BHAVAN, 9 BAHADUR SHAH NEW DEiHI 110002 Gr3 May 1972 IS I 4518 ( Part II,) - 1971 Indian Standard METHOPS OF .TEST FOR STYRENE-BUTADIENE RUBBERS PART II DETERMINATION OF SOLVENT AND OIL CONTENT Rubber Chairman SHRI EXTRACT 42 Sectional Committee, CDC Representing LALIT MOHANJAMNADAS Vice-Chairman The Cosmos India Rubber Works Pvt Ltd, Bombay Bata Shoe Co Pvt Ltd, Calcutta SHRI P. P. M~KHERJEE Members SHRI S. C. NANDY( Altemute to Shri P. P. Mukherjee ) Rubber Research Institute of India, Kottayam SHRI V. K. BHASKARAN NAIR SHRI K. C. ANANTH( Alternate ) Indian Rubber Manufacturers' Research Association, DR M. L. BHAUMIK Bombay Rubber Marketing Arakkunnam Co-operative SHRI J. C. CHALY Society Ltd, Arakkunnam ( Keraia ) Ministry of Defence ( DGI ) SHRI B. H. DALAL SHRI M. KUMARAN ( Altemute ) National Test House, Calcutta DR D. K. DAS SHRI A. GHOSH ( Alternate ) Ministry of Defence ( R & D ) SHRI S. L. GANDHI SHRI M. G. BHARGAWA ( Alternate ) Peirce Leslie & Co Ltd,. Coimbatore SHRI P. K. MADHAVA MXNON Indian Rubber Indnstnes Association, Bombay DR K. N. MODAK SHRI B. B. SANGTANI ( Altemnte) Assoga;:nntiof Rubber Manufacturers in India, SHRI S. MUKHERJEE SHRI L. N. SATHIA( Alternate ) SKRI P. MUKUNLA MENON SHRI K. K. NAIR SHRI K. A. PAUL ( Alternate ) .%IRI hf. AI. PATEL Rubber Board, Kottayam Plantation Corporation of Kterala Ltd, Kottayam Synthetiu & Chemicals Ltd, Bombay Kottayam SHRI V. C. NANAVATI ( A&mate ) Association of Planters of Kerala, SHRI R. H. PAYLOR Madras Rubber Factory, Madras SHRI K. M. PHILIP SHRI D. RAGHUNATH DR N. V. C. RAO SHRI K. C. SEKAR National Chemical Laboratory ( CSIR), Poona Direrrt;elzenflill of Techmml Development, Padinjearekara Agencies ( Pvt ) Ltd. Kottayam ( Continued on page 2 ) BUREAU MANAK OF INDIAN STANDARDS MARG T~HAvAN, 9 BAHADUR SHAH ZAFAR NEW DELHI 110002 IS : 4518( Part II ) - 1971 ( Continuedfrom fiage 1 ) Members Kanyakumari SHRIS.SUBRAM.~NIAN SHRI A. L. N. RAMANATHAN CH~rrX4a ( Representing Distt Planters' Association, Nagersoil Rubber Dealers' Association, Kottayam SHRI K. C. THOMAS SHRI T. D. MATHEW ( Altemute ) United Planters' Association Coonoor SHRI M. M. MUTHIAH ( Alkmate ) Director General, IS1 ( Ex-oficio SHRI D. DAS &PTA, Director ( Chem ) SHRI M. M. VARCHESE Secretary SHRI SATISHCHANDER Deputy Director ( Chem ), ISI of Afternote ) Southern India, Member ) Methods of Testing Subcommittee, CDC 42 : 1 Rubber Board, Kottayam SHRI V. K. BHASKARAN NAIR SHRI K. C. ANENTH(Alternate) Bayer ( India ) Ltd, Bombay DR S. N. CHAKRAVAR~ SHRI R. R. PANDIT ( Alternate ) National Test House, Calcutta DR D. K. DPS SHRI A. GHOSH ( Alternate ) Indian Rubber Regenerating Co Ltd, Thana SHRI W. G. DESAI Monsanto Chemicals of India Pvt-Ltd, Bombay Da A. S. ___._. _. GHAG _ The Cosmos India Rubber Works Pvt Ltd, Bombay SHRI P. D. KHEMKA SHRI PULINL. KINAR~WALA ( Alternate ) Peirce Leslie & Co Ltd. Coimbatore SHRI P. K. MADHAVA MENON L. G. Balakrishnan & Bros Pvt Ltd, Coimbatore SHRI N. S. NAGARAJA RAO SHRI MURARI ~ARMAICAR ( Altematc) Synthetics & Chemicals Ltd, Bombay SHRI M. M. PATEL SHRI P. P. MAHALINGAM ( Alternate ) Dunlop India Ltd, Calcutta SHRI L. N. SATHIA SHRI I. DANIEL ( Al&mute ) Pandinjarekara Agencies ( Pvt ) Ltd, Kottayam SHRI K. C. SEKAR 2 IS : 4518( Part II ) - 1971 Indian Standard METHODS OF TEST FOR STYRENE-BUTADIENE RUBBERS PART II DETERMlNATiON OF SOLVENT AND OIL CONTENT EXTRACT 0. FOREWORD 0.1 This Indian Standard ( Part II ) was adopted by the Indian Standards Institution on 29 October 1971, after the draft finalized by the Rubber Sectional Committee had been approved by the Chemical Division Council. 0.2 Part I of this standard covers the methods of test for determination the following: of a) Volatile matter by mill method ( SBR : 1 ) and mill oven method (SBR : 2 ), b) Total ash ( SBR : 3 ), c) Organic acid content ( SBR : 4 ), d) Soap content ( SBR : 5 ), e) Antioxidants f) ( SBR : 6 ), Bound styrene ( SBR : 7 ), and g) Mooney viscosity ( SBR : 8 ). 0.3 The methods prescribed in this standard take into consideration the recommendations of International Synthetic Rubber Producers Association. Designation Besides, assistance has also been derived from ,ASTM D 1416-67 T ` Chemical analysis of synthetic elastomers ( solids tyrenebutadiene copolymers ) ' issued by the American Society for Testing and Materials and Draft IS0 Recommendation No. 1407 `Determination of solvent extract in natural and synthetic rubber' issued by International Organization for Standardization. 0.4 In reporting the result of a test or analysis made in accordance with this standard, if the final value, observed or calculated, is to be rounded off, it shall be done in accordance with IS : 2-1960*. *Rules for rounding off numerical values ( revised ). 3 IS : 4518 (Part II ) - 1971 1. SCOPE. 1.1 This standard prescribes the methods of test for determining solvent extract ( SBR : 9 ) and oil content ( SBR : 10 ) of raw styrene-butadiene rubbers. 2. QUALITY OF REAGENTS and distilled water ( see 2.1 Unless otherwise, specified `pure chemicals' IS : 1070-1960* ) shall be employed in tests. NOTE- ` Pure chemicals affect the result of analysis. 3. METHOD ' shall mean chemicals that do not contain impurities which OUT SAMPLES ,with the FOR TAKING .3.1 The method method prescribed for taking out samples shall be in accordance in 3 of IS : 4518 ( Part I )-1967t. Specification for water, distilled quality ( revised). tMethods of tests for styrene-butadiene rubbers ( SBR ): Part I. 4 lSt4518(PWII)-19'ft DETERMINATION OF SOLVENT (SBR:9) EXTRACT 0. GENERAL 0.1 Two' methods~are prescribed here. Method A is based on the method being considered by ISO/TC 45 Rubber, and is recommended as a reference method. Method B is an alternate method and is recommended for routine analysis. 1. SCOPE 1.1 This method is intended to determine the various organic constituents It will give the combined amount of in the rubber as solvent extract. rosin and fatty acids, soaps, oil extenders, defoamer tars, antioxidants and other uncombined organic constituents. NOTE-The rubber hydrocarbon can alao be estimated by subtracting the sum of the ethanol-toluene azeotrope (ETA) extract. the total ash, and the volatile matter from 100. METHOD A 2. OUTLINE OF THE METHOD 2.1 A weighed test portion of the rubber is extracted with ethahol-toluene The solvent is distilled off and azeotrope solvent in a suitable apparatus. the residue is dried and weighed. 3. APPARATUS 3.1 Extraction Apparatus -The extraction apparatus is of the reflux type with the condenser placed immediately above the cup which holds the rubber, The cup is situated in the vapour of the boiling solvent and is emptied by a siphon. The apparatus is of glass except in patterns where an extraction cup is suspended from the end of condenser and, in that case, platinum wire is used for the suspension. The apparatus fits together without the use of cork, rubber or metal and in such a manner that loss of vapour during extractioh does not exceed 20 percent of the extracting liquid. 3.1.1 Suitable tvnes of apparatus are shown in Fig. 1. 3.2 Filter Paper or Cloth - Acid washed hardened filter paper or nylon cloth of open weave and continuous filaments. 5 175mm MtN 1YPE I A -joint 34135 TYPE 2 FIG. 1 &cTRACTION APPARATUS 6 IS:4518(PartII)--I971 4. R&AGENTS 4.1 Ethanol-Toluene Azeotrope ( ETA ) - Mix 70 volumes of ethanol (see IS: 321-1964, ) and 30 volumes of toluene ( set IS : 537-1967t). Reflux for four hours over freshly calcined calcium oxide. Distil and collect a middle fraction with a boiling range between 76.2 to 77.2% at atmospheric pressure. 5. PROCEDURE 5.1 Pass the rubber six times between the rolls of a laboratory mill set to a nip not exceeding 0~5 mm. Cut from the sheet a test portion estimated to weigh 3 to 5 g depending on the material to be tested and weigh to the nearest 0.01 g. If it is not possible to pass the sample through the mill, the sample may be cut into pieces less than 1 mm per side. Roll the weighed test portion in filter paper or nylon cloth to form a loose roll from which the rubber cannot fall and so that no part of the rubber is anywhere in contact with any other part of the rubber. Place the roll in the extraction cup ofthe extraction apparatus and pour into the extraction flask sufficient solvent to fill the extraction cup two or three times. Assemble the apparatus and ,adjust the temperature so that the distilled quantity of solvent fills the extraction cup ten to twenty times per hour. The extraction time shall be 16.0 i 0.5 hours. Evaporate off the solvent in a weighed vessel, preferably in the extraction flask, at about 100°C. Dry the flask for two hours at 100 f 2°C in an oven. Cool in a desiccator and weigh to the nearest 0.001 g. NOTE - The results obtained may be different depending on the method of sample preparation. 6. CALCULATION 6.1 Solvent extract, percent by mass = where Ml = mass in grams of the extraction flask and extract, Ma = mass in grams of the extraction flask, and mass in grams of the test portion. M,= 7. REPORT 7.1 The report shall include the following: a) Proper identification of sample, b) Sample preparation, *Specification for absolute alcohol ( rcviscd). tspecification for toluene, pure, nitration grade (JsrSr r&a). %--MI M a x 100 7 IS t 4518 ( Part II ) - 1971 c) Type of extraction apparatus, and d) Result obtained. 8. OUTLINE OF THE METHOD 8.1 Thin, narrow strips of the dried rubber are extracted three times with 100 ml of hot ETA ( see 10.1) solvent for one hour each and rinsed three times with 10 ml portions of ETA solvent. Although two extractions are sufficient for non-pigmented rubbers, three extractions are necessary for oil-masterbatch rubbers. The extracted rubber is boiled with 25 ml of acetone, decanted, and dried. The difference in weight between the original sample and the extracted sample is the weight of ETA extract, 9. APPARATUS 9.1 Asbestos Mat 9.2 Filter Paper 9.3 Hot plate 9.4 WideMouth 9.5 Wire Gauze 10. REAGENTS 10.1 Ethanol-Toluene Azeotrope ( ETA-) - Prepare by mixing 70 volumes of ethyl alcohol and 30 volumes of toluene, refluxing the mixture for four hours over calcium oxide and distilling. Discard the first and last portion, keeping only that distillate coming over within a range of 1°C. -Distilling may be avoided by using absolute alcohol. NOTE 10.2 Acetone conforming to IS : 170-1966'. Flask 400 to 500 ml capacity. 11. PROCEDURE 11.1 Dry the sample in accordance with the method prescribed in ( SBR : 1) nor ( SBR : 2 ) of IS : 4518 ( Part I )-1967t. Sheet it to a thickness of 0.5 mm or less. Cut approximately 6 g of the dried, sheeted material into strips not wider than 10 mm nor longer than 50 mm. NOTE-Ensure ~that the strips are 0.5 mm or less in thickness in order to secure complete extraction. *Specification for acetone (J;rst reuision ). tMethods of tests for styrene-butadiene rubbers ( SBR ): Part I. 8 IS : 4518 ( Part II ) - 1971 11.2 Accurately weigh 6 g sample of the dried strips. Add 100 ml of ETA ( see 10.1) solvent to the wide-mouth flask. Add each strip of the weighed sample separately to the flask, swirling the flask after each addition so that each strip is thoroughly wetted with the solvent to avoid sticking. To prevent the sample from sticking to the wide-mouth flask, place a filter paper in the bottom of the flask and use a wire gauze or Reflux the contents of asbestos mat between the flask and the hot plate. the wide-mouth flask on the hot plate for one hour. After refluxing, decant the ETA extract and discard it. Add a second 100 ml portion of the ETA solvent to the rubber sample and reflux again for one hour. Again decant the ETA extract and discard it. Add a third 100 ml portion of the ETA solvent to the rubber sample and reflux again for one hour. For the third time., decant the ETA extract and discard it. Rinse the sample with three successive 10 ml portions of the ETA solvent. Add approximately 25 ml of acetone to the rubber sample remaining in the wide-mouth flask. Heat the acetone to gentle boiling and boil it for approximately 5 minutes. Decant the acetone and transfer the extracted sample to a tared watch`glass. Dryit to constant weight at 105°C. NOTE-This oven. can be done in 1 hour at 105"C and 725 mm of vacuum in a vacuum 13. CALCULATION 13.1 ETA where extract, percent = 100 (Ml-%) M 1 Ml = mass in grams of the original dry sample, and M, = mass in grams of the extracted sample. 9 IS : 4518 ( Part II ) - 1971 DETERMINATION OF OIL CONTENT IO) (SBR: 1. SCOPE 1.1 This method covers the estimation of the oil content of oil extended ( SBR)-rubbers and carbon black masterbatches. It is intended for use in checking for uniformity having loading up to 75 -parts per hundred of rubber ( phr). METHOD 2. OUTLINE OF THE METHOD A 2.1 The ETA extract of the dried rubber is determined. The oil content of the masterbatch ise stimated by subtracting from the ETA extract the total of the ETA soluble constituents other than oil. This difference is an estimate of the oil content. 3. PROCEDURE. 3.1 Determine mass of original ETA extract in styrene butadiene rubbers as percent dry sample ( A ) in accordance with ( SBR : 9 ). by 3.2 Determine organic acid in styrene butadiene rubbers as percent by mass of original dry sample ( B ) in accordance with (SBR : 4) [ see IS : 45 18 ( Part I )-1967* 1. 3.3 Determine soap content in styrene butadiene rubbers as percent by mass of original dry sample ( C ) in accordance with (SBR : 5) [ see IS : 4518 ( Part I )-1967* 1. 3.4 Determine antioxidants in styrene butadiene mass of original dry sample ( D ) in accordance IS : 4518 ( Part I )-1967*]. NOTE - If antioxidant/antiozonants may be calculated: D=-;where E = nominal antioxidant added to rubber phrt; and F = ;n;zrbatch recipe, in parts = 100 + phrt of oil $ phrt of carbon rubbers as percent by with ( SBR : 6 ) [see ( D ) cannot be determined, the following value x100 `Methods of tests for styrene-butadiene tPart.s per hundred of rubber. rubbers ( SBR ): Part I. 10 IS : 4518( Part II ) - 1971 4. CALCULATION 4.1 Oil content where percent by mass = A ( B + C +D ) A = ETA extract, C = soap, percent percent by mass of the original dry sample; and B = organic acid, percent by mass of the original dry sample; by mass of ihe original percent dry sample; D I antioxidant/antiozonant, dry sample. by mass of the original METHOD 5. OUTLINE OF THE METHOD B 5.1 The acetone extract of the dried rubber is determined. The oil content ~of the masterbatch is estimated by subtracting from the acetone extract the total of the acetone soluble co@ituents other than the oil. The difference is an estimate of the oil content. 6. APPARATUS 6.1 Extraction Apparatus general 6.2 6.3 type prescribed The extraction in ( SBR : 9 ), to maintain flask and condenser is of the Hot Plate - Surface a temperature of at least 100°C. Vacuum Oven 7. PROCEDURE 7.1 Dry the sample in accordance with the method prescribed in SBR: 1 Sheet it to a thickness of O-5 or ( SBR : 2 ) of IS : 4518 ( Part I )-1967*. mm or less. Cut approximately 6 g of the dried, sheeted matetial not wider than 10 mm and not longer than 50 mm. NOTE-Ensure that complete extraction. into strips the strips are 0.5 mm or less in thickness in order to secure 7.2 Accurately weigh a 2 g sample of the dried strips. Add 200 ml of Add each strip of the weighed sample acetone to a 400 to 500-ml flask. separately to the flask, swirling the flask after each addition so that peach strip is_thoroughly wetted with solvent to avoid sticking. To prevent the sample from sticking to the flask, place a filter paper in the bottom of the flask, and use a wire gauze or an asbestos mat between the flask and the hot plate. Reflux the contents of the flask on the hot plate for 30 minutes. I *Methods of tests for styrene-butadiene rubbers ( SBR ) : Part I. 11 IS : 4518( Part II ) - 1971 Decant the acetone extract and discard it, but make sure that all the Add a second 200 ml portion of acetone to rubber remains in the flask. Decant the acetone exthe rubber sample and reflux again for 30 minutes. tract and discard it, but make sure that all the rubber remafns in the flask. Add a third 200 ml portion of acetone to the rubber sample and reflux again for 30 minutes. For the third time, decant the acetone extract and discard it. Rinse the sample with 10 to 20 ml of acetone. Decant the Dry the acetone and transfer the extracted sample to a tared watch glass. rubber to constant weight in a vacuum oven at 105°C and minimum Weigh the dry rubber. 685 mm of mercury vacuum. 8. CALCULATION 8.1 Oil content, where percent by mass = lOO(;-*)-(BfC+D) A = mass of the original X = mass of the extracted c = soap, percent _D = antioxidant, dry sample; sample; B = organic acid, percent by mass ( SBR : 4 ); by mass ( SBR : 5 ) ; and percent by mass ( SBR : 6 ). NOTE- If antioxidant cannot be determined, the following value may be calculated: D=+ x 100 E = nominal antioxidant added to rubber, phr*; and F = ;;;rbatch recipe, in parts = 100 + phr* of oil + phr* of carbon *Parts per hundred of rubber. 12 BUREAU OF INDIAN STANDARDS Headquarters: Manak Bhavan, 9 Bahadur Shah Zafar Marg, NEW DELHI Telephones: 323 0131,323 8375,323 9402 Fax :Ql 11 3234062.91 11 3239399 110002 Central Laboratory : Industrial Area, Sahibabad 201010 Telegrams : Manaksanstha (Common to all Offices) Telephone 8-77 00 32 Plot No. 20/Q, Site IV, Sahibabad Regional OtTices: Central *Eastern Northern Southern : Manak : l/14 : C.I.T. Bhavan, 9 Bahadur Shah Zafar Marg, NEW DELHI 110002 CALCUTTA 700054 323 76 17 337 66 62 60 36 43 23523 15 CIT Scheme Vii M, V.I.P. 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